Bis-quaternary ammonium compounds



United States Patent 3,453,281 BIS-QUATERNARY AMMONIUM COMPOUNDS Donald M. Burness, Kenneth C. Kenuard, and Bernard C. Cossar, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey N 0 Drawing. Continuation-impart of application Ser. No. 848,527, Oct. 26, 1959. This application Aug. 22, 1962, Ser. No. 218,572

Int. Cl. C07d 29/06, 31/48 U.S. Cl. 260-2934 18 Claims This invention relates to novel quaternary salts which contain two quaternary ammonium radicals linked together through a chain of carbon atoms which is interrupted by at least two SO radicals.

This application is a continuation-in-part of our application Ser. No. 484,527, filed Oct. 26, 1959, now patent No. 3,067,437.

The sulfur-containing bis-quaternary salts of our invention are particularly useful in increasing the sensitivity of photographic silver halide emulsions.

A number of methods have been previously described for increasing the sensitivity of photographic silver halide emulsions, other than methods of optical or spectral sensitization which involve the incorporation of certain colored compounds or dyes in the emulsions. The incorporation of such dyes in the emulsions increases the optical range of sensitivity, and for this reason such dyes are commonly referred to as optical or spectra-l sensitizing dyes. It is also well known to increase the sensitivity of photographic emulsions by addition of sulfur compounds capable of reacting with silver salts to form silver sulfide, or with reducing agents (compounds of these types are also naturally present in gelatin), or with salts of gold or other noble metals, or with combinations of two or more of the aforementioned compounds generally known as chemical sensitizers. Such chemical sensitizers are believed to react with the silver halide to form, on the surface of the silver halide, minute amounts of silver sulfide or of silver or of other noble metals, and these processes are capable of increasing the sensitivity of developing-out emulsions by very large factors. The process of chemical sensitization, however, reaches a definite limit beyond which further addition of sensitizer, or of further digestion with the sensitizer present, merely increases the fog of the photographic emulsion with constant or decreasing speed.

We have now found a means of further increasing the sensitivity of photographic emulsions which may be applied even though the ordinary processes of chemical sensitization have been carried to the effective limit of the photographic emulsion in question. Our process is to be distinguished from hypersensitization, which is produced by bathing a finished coating with water or with solutions of ammonia, amines or silver salts. Such processes act primarily on optically sensitized photographic emulsions and tend to increase the free silver ion concentration of the emulsion and greatly diminish its stability. Our process is also to be distinguished from hypersensitization by mercury vapor, which gives a transitory effect which is lost on storage of the film. The compounds used in our invention do not appear to be chemical sensitizers in the usual sense, since they increase speed by their presence during exposure and processing and require no digestion with the photographic emulsion to produce an increase in speed, nor does their chemistry indicate that they are likely to react with silver halide under normal emulsion conditions.

The novel sensitizers of our invention are quite unique in that the effects produced are additive in photographic emulsions which have already been sensitized to their optimum, or near-optimum, with conventional chemical sensitizers, such as labile sulfur compounds. The novel sensitizers of our invention, however, can be used to sensitize photographic silver halide emulsions containing no other sensitizers, if desired. The novel sensitizers of our invention are not strictly chemical sensitizers, since chemical sensitizers do not generally provide the additive effects of the type mentioned.

It has been further found that the novel sensitizers of our invention can be usefully employed in photographic developing solutions, such as those intended for the production of a black-and-white silver image, as well as those intended for the production of a photographic dye image. Typical black-and-white developing agents which can be used in conjunction with our novel compounds are hydroquinone, N-methyl-p-aminophenol salts, chlorohydroquinone, 4' methylphenylhydroquinone, 4 phenyl catechol, 3-pyrazolidones, e.g., 1-phenyl-3-pyrazolidones, 1 phenyl-4-methyl-3-pyrazolidones, l-p-tolyl-4,4-dimethyl-3-pyrazolidones, 1 phenyl-4,4 dimethyl 3 pyrazolidones, etc. Useful color-forming developers include the phenylenediamines and substituted derivatives thereof containing at least one free amino group, such as p-phenylenediamine, N,N-diethyl-p-phenylenediamine, 3-methyl-N,N- diethyl-p-phenylenediamine, etc.

It is, therefore, an object of our invention to provide novel compounds which are useful in sensitizing photographic silver halide emulsions. Another object is to provide methods for making these novel compounds. Still another object is to provide photographic developing compositions for silver halide containing these novel compounds. Other objects will become apparent from a consideration of the following description and examples.

The new compounds of our invention include those represented by the following general formula:

wherein R and R each represents an alkylene group, such as ethylene, trimethylene, tetramethylene (butylene), methyl-substituted ethylene, methyl-substituted trimethylene, pentamethylene, ethyl-substituted tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, etc. (e.g., a hydrocarbon alkylene group containing from about 2 to 10 carbon atoms), d represents a positive integer of from about 1 t0 3, Q represents an organic quaternary ammonium group, such as pyridinium, picoliniurn, collidiuium, N- methylpiperidinium, N-ethylpiperidinium, triethyl ammonium, diethylrnethyl ammonium, tripropyl ammonium, diethylbutyl ammonium, N-methylmorpholinium, etc., and X represents an acid anion or radical, such as perchlorate, p-toluenesulfonate, benzenesulfonate, methylsulfate, ethylsulfate, bromide, etc.

An especially useful group of sensitizing compounds embraced by Formula I above is that represented by the following general formula:

wherein Q X and d each have the values given above, and m and it each represents a positive integer of from about 2 to 10.

A useful group of compounds according to our invention containing heterocyclic quaternary ammonium groups is the group represented by the following general formula: Ib. ,""\G9 sar'.

q, I' I(CH2)m[SO2(CH2)nldSO2(CH2)[xi-N git-2X wherein d, m, n and X each have the values given above, and Q represents the non-metallic atoms necessary to complete a heterocyclic monoazine ring, such as pyridine, picoline, collidine, etc.

Another group of useful sensitizers embraced by Formula In is that represented by the following general formula Ic. G9 69 9 R2N-(CII2)...[SO -(C I11) n] |SO2(CII2)m-N 2' wherein d, m, n and X each have the values given above, and R R and R each represents a lower alkyl group, such as methyl, ethyl, propyl, butyl, etc.

The compounds of Formulas I-Ic above can advantageously be prepared according to methods which have been previously described in the prior art. For example, the components of Formula lb can be prepared by condensing the hydroxy compounds of Williams and Cossar U.S. application Ser. No. 843,638, filed Oct. 1, 1959, with an organic sulfonyl chloride, followed by condensation of the resulting organic sulfonic ester with a heterocyclic amine, such as pyridine, picolines, collidines, etc. The resulting thioether compound can then be oxidized t the desired sulfone by treatment with hydrogen peroxide in acetic acid solution, or by other oxidizing agents, such as hypochlorous acid, and the like. The compounds of Formula Ia, wherein Q represents the non-metallic atoms necessary to complete a piperidine ring, or the like, can be prepared by quaternating a compound selected from those represented by the following general formula:

wherein Q, d, m and it each have the values given above with an organic sulfonic ester, such as dimethyl sulfate, diethyl sulfate, methyl benzenesulfonate, methyl p-toluenesulfonate, etc. The resulting thioether compound can then be oxidized to the desired sulfone by treatment with hydrogen peroxide in acetic acid solution, or by other oxidizing agents, such as hypochlorous acid, and the like. In like manner, the compounds of Formula can be prepared by quaternating a compound selected from those represented by the following general formula:

wherein R R d, m and 11 each have the values given above with an organic sulfonic ester, such as dimethyl sulfate, diethyl sulfate, methyl benzenesulfonate, methyl p-toluenesulfonate, etc. The resulting thioether compound can then be oxidized to the desired sulfone by treatment with hydrogen peroxide in acetic acid solution, or by other oxidizing agents, such as hypochlorous acid, and the like.

Still another useful group of sensitizers embraced by our invention includes those represented by the following general formula:

Id. R259}? bonamtsorwnz)nldsozronam-d \JH wherein R 0, m, n and X each have the values given above, and J and J together represent the non-metallic atoms necessary to complete a pyridine ring, which may contain conventional substituents, such as methyl, ethyl, chlorine, etc. In the compounds of Formula Id, it will be noted that the quaternary nitrogen atom is not attached to the terminal carbon atoms of the intercyclic chain, as contrasted with the nitrogen atoms of Formula Ib, which are attached to these carbon atoms. The compounds of Formula Id can be prepared in a manner similar to that outlined above. For example, these compounds can be prepared by condensing together a dihalogenated alkane, or thia-alkane, with a pyridylalkanethiol of the following general formula:

wherein I, I and 111 have the values given above. The resulting thioether compound can then be quaternated with an organic sulfonic ester, such as those illustrated above, followed by oxidation with an aqueous solution containing hydrogen peroxide and acetic acid or another oxidizing bath, such as is illustrated above.

The preparation of the compounds useful in practicing our invention and the necessary intermediates are described in the following examples.

EXAMPLE l.1,18-DI-P-TOLUENESULFONOXY- 4,1 S-DITHIAOCTADECANE EXAMPLE 2.4,15-DITHIAOCTADECANE-1,18- BIS (PYRIDINIUM PERCHLORATE) A solution of 21 g. of the product from Example 1 and 10 g. of pyridine was heated at the boiling point for 10 minutes, cooled, and poured into ether. The solid was filtered, washed with ether, dissolved in water, and treated with an excess of sodium perchlorate. The yield of colorless solid was 13 g. (the intermediate p-toluenesulfonate salt may be used directly in the next step).

EXAMPLE 3.4,4,l5,15 TETROXO 4,15 DITHIA- OCTADECANE 1,18 BIS(PYRIDINIUM PER- CHLORATE) The 13 g. of product from Example 2 were dissolved in 500 ml. of acetic acid, heated to 60 C., and 15 g. of 30 percent hydrogen peroxide added. After 24 hours at 60 C., the solvent was removed at reduced pressure and the product recrystallized from acetone; yield, 4 g.; M.P. 86 C.

Analysis.Calcd. for C H42Cl2N O12S2: C, H, 5.9; N, 3.9. Found: C, 44.4; H, 6.0; N, 3.8.

EXAMPLE 4. 4,4,10,1o TETROXO 4,10 DITHIA- TRIDECANE 1,13 BIS(PYRIDINUM PERCHLO- RATE) (a ofirnmonzns0, camsozwnngio ns-zolol By a procedure similar to that of Examples 13, the title compound having M.P. 235 C. (dec.) was prepared.

Analysis.Calcd. for C21H32C12N2012S2: C, H, 5.0; N, 4.4. Found: C, 38.5; H, 5.1; N, 3.6.

EXAMPLE 5.-7,7,l8,l8 TETROXO 7,18 DITHIA- TETRACOSANE 1,24 BIS(PYRIDINIUM P TOSYLATE) By the method of Examples 1-3, this compound having melting point l30 C. was prepared.

Analysis.--Calcd. for C I-I N O S C, 60.0; H, 7.3; N, 3.0; S, 13.7. Found: C, 58.4; H, 7.6; N, 3.1; S, 13.5.

EXAMPLE 6.4,4,8,8 TETROXO 4,8 DITHIAUN- DECANE-1,l1-BIS(PYRIDINIUM PERCHLORATE) 6 This compound, prepared according to Examples 1-3 This was obtained as in Examples 9 and 3 by use of and recrystallized from nitromethane, melted at 203- 3-picoline as an uncrystallizable oil. 205 C.

EXAMPLE 14.7,7,13,13-TETRAOXO-7,13 DITHIA- CwHzaClzNzomsfi 374; NONADECANE-l,19-BIS(4-PICOLINIUM P-TOLU- 4.6, N, 4.6. Found: C, H, N, 4.6. 5

EXAMPLE 7.7,7,10,l0,13,13-HEXOXO-7,10,13 TRI- This compound, obtained as in Examples 9 and 3 from THIANONADECANE-1,19BIS(PYRIDINIUM PER- 10 4-pic0line, melted at 7980 C. CHLORATE) EXAMPLE 15.--1,18-DI- -PYRIDYL 4,15 DITHIA- ofim twnmsoxonmsoiwmhsozwmm ofinszoioi gg gggg BISMETHO P TOLUENESU-L' This compound, prepared in the usual manner, melted With decomposition at ca. 160 C. H Ii (CHQ)3S(OH2)1DS(QH,)3 \N OH2 Analysis.-Calcd. for C25H42C12N2O14S3: C, H, 69 G3 5.4; N, 3.6; S, 12.4. Found: C, 39.2; H, 5.6; N, 3.0; S, ,9 G A solution of 44.4 g. of 1,18-di-y-pyridyl-4,IS-dithia- EXAMPLE 8.--7,7,13,13 TETROXO 7,13 DITI-IIA- Octadecane and 37.2 g. of methyl p-toluenesulfonate in NONADECANE-1,19BIS (PYRIDINIUM P TOLU- 200 ml. of ethanol was refluxed for 4 hours. Evaporation ENESULFONATE) of the solvent and recrystallization from acetone produced Q, G) e colorless crystals of M.P. 100102 C. C H5N(CHz)sSOz(CH2)5SO2( H2)tNC5H5'2(p) CH3CaH4-SO3 'Y This compound, p p as in Examples melted TETRAOXO 4,15 DITHIAOCTADECANE BIS- at METHO-P-TOLUENESULFONATE Analysis.Calcd. for C H N O S C, 56.7; H, 6.7; N, 3.2; S, 14.7. Found: C, 56.0; H, 6.7; N, 3.4; S, 15.1. CH3 N/: 0 9 0, 0 o, o11 N c]1, EXAMPLE 9.-7,13 DITHIANONADECANE 1,19- 9 m /B BIS(PYRIDINIUM P-TOLUENESULFONATE) P CHPCSH4SO3G eoflscflflcoflm 9 p A solution of 15 g. of the sulfide from Example 15 C H N(CH S(CH2)5S(CH2)sNC5H -2(p)CH:4CaH4S03 and 5 g. of 30 percent hydrogen peroxide in glacial acetic (Intermediate f Example A solution f 34 f acid was heated at 60 C. for 24 hours. The solvent was 7,13-dithia-1,19-nonadecanediol in 100 ml. of pyridine was moved at reducifd preisurei h resldue dlssolved m treated with 50 g. of p-toluenesulfonyl chloride at 20 methanol decolonzefi Wlth Fctlvated and the C and kept cold overnight. The mixture was worked solvent removed to give the light amber, o1ly sulfone. up as in Example 1 and the resulting oil boiled for 15 Analysls--calci for C42H60N2S4O101 C, 57.3; H, 6.8; minutes in excess pyridine. The solution was cooled and 32; Found: 564; H, N, 31;

poured into ether to give a colorless, hygroscopic solid 40 EXAMPLE 17 3 14 DITHIAHEXADECANE 1 1 of after drying in vacuo- BIS(N-METHYLPIPERIDINIUM P-TOLUENESUL- Analysis.Calcd. fOI' C41H5 N S4O5: C, N, 3.5; s, 15.9. Found: c, 61.0; H, 7.3; N, 3.2; s, 15.6. CH3 CH3 EXAMPLE 10.7,10,13-TRITHIANONADECANE- S CH S OH CH E S BIS(PYRIDINIUM PERCHLORATE) 45 Ce e o CgH fllHfias(CH2)2S(CHg)g)gSCHz)aI ?C H5-C1O4 ossomk'cmm) (Intermediate for Example 7.) The p-toluenesulfonate A Solution f 48.7 of 11643i1 piperidy1) 3,14 di salt, obtained from 7,10,13-tr th1a-1,19-nonadecaned o thiahexadecane and 53 g. of methyl p-toluenesulfonate in as in Example 9, Was treated 1n aqueous solutlon with methanol was refluxed for 16 hours, the solvent removed excess sodlu'm Perchlorate- Removal of the solvent and and the residue dissolved in ethanol. Precipitation with recrystallization from ethanol gave a crystallme solid of ether produced 86 of crystalline solid of M'P.

M-P. 235 C. (dec.) 1570 C.

EXAMPLE 11.7,18-DI'IHIATETRACOSANE-1,24- Analysis.-Calcd. for C H N S O C, 60.0; H, 8.5; BIS(PYRIDIN[UM P-TOLUENESULFONATE) 55 N, 3.5; S, 16.0. Found: C, 59.0; H, 8.5; N, 3.1; S, 16.3.

EXAMPLE 18.3,l4 DITHIA-3,3,14,14-TETRAOXO- HEXADECANE 1,16 BIS (N METHYLPIPERI- DINIUM p-TOLUENESULFONATE) (Intermediate for Example 5.) Prepared as in Example 9 this compound, recrystallized from ether-ethanol, melted at 143-145 C. CH3 CH3 j EXAMPLE 12. ,7,13,13-TETRAOXO-7,13 DITHIA- S NwflmsOKCHQWSOMCHm-EVK S NO NADECANE- 1 19-BIS (Z-PICOLINIUM P-TOLU- e 83 ENESULFONATE) O SCuH1-CH3(ZJ) O3SCflH4-CH3 (p) a q f Similar to that P 9 and 3 and A solution of 60 g. of the sulfide of Example 17 and fi 531 m place ofdpyndme thls compound of 36 ml. of 30 percent hydrogen peroxide in acetic acid was Prepare was heated at 5060 C. for 16 hours. The solvent Was EXAMPLE 13.7,7,13,13-TETRAOXO-7,13 DITHIA- removed at reduced pressure, the residue dissolved in NONADECANE-I,l9-BIS(3-PICOLINIUM P-TOLU- ethanol and precipitated with ether, then recrystallized ENESULFONATE) from ethanol; M.P. 178 C.

7 Al1alysis.Calcd. for C H N S O 2 C, H, N, 3.2; S, 14.8. Found: C, 54.7; H, 7.9; N, 2.9; S, 14.4.

EXAMPLE l9.-3,l4 DITI-IIA-3,3,l4,l4-TETRAOXO- HEXADECANE 1,16 BIS (DIETHYLMETHYL- AMMONIUM p-TOLUENESULFONATE) This compound, a viscous oil, was obtained by the procedures described in Examples 17, 18 and 20 from ,B-diethylaminoethanethiol.

The following examples will serve to illustrate the method of preparing the two intermediates required for Examples 15 and 17 above.

EXAMPLE 20.-l l 8-DI-y-PYRIDYL-4, 15 DITHIAOCTADECANE To a solution of 9.2 g. of sodium in 500 ml. of absolute methanol were added 16.6 g. of 'y-3-mercaptopropylpyridine, followed by 60.2 g. of 1,10-dibromodecane. After a 2-3 hour reflux period, one liter of water was added, the mixture extracted with chloroform, the extracts decolorized with carbon, dried over magnesium sulfate and evaporated to a yellow crystalline mass.

EXAMPLE 21 .1,16-BIS( l-PIPERIDYL) -3 ,14- DITHIAHEXADECANE This was prepared by the procedure of Example 20, using 9.2 g. of sodium, 500 ml. of methanol, 50 g. of fl-l-piperidinoethanethiol and 60 g. of 1,10 dibromodecane. The product, an oil, weighed 62 g.

The sensitizing compounds of our invention can be added to ordinary photographic silver halide emulsions for the purpose of increasing the sensitivity thereof, as has been indicated above.

The preparation of photographic silver halide emulsions involves three separate operations: (1) emulsification and digestion of silver halide, (2) the freeing of the emulsion of excess water-soluble salts, usually by washing with water, and (3) the second digestion or after-ripening to obtain increased emulsion speed or sensitivity. (Mees, The Theory of the Photographic Process, 1954). The sensitizers of our invention can be added to the emulsion before the final digestion or after-ripening, or they can be added immediately prior to the coating. Our new photographic sensitizers require no special final digestion or after-ripening.

The particular quantity of sensitizer used in a given emulsion can vary, depending upon the effects desired, degree of ripening, silver content of the emulsion, etc. The amount used is also dependent upon the particular ssage at which the sensitizer was added during the preparation of the emulsion. We have found that generally from about 50 mg. to about g. of sensitizer per mole of silver halide are quite adequate to accomplish the desired sensitization.

The sensitizers of our invention can be added to photographic emulsions using any of the well-known techniques in emulsion making. For example, the sensitizers can be dissolved in a suitable solvent and added to the silver halide emulsion, or they can be added to the emulsion in the form of a dispersion similar to the technique used to incorporate certain types of color-forming compounds (coupler) in a photographic emulsion. Techniques of this type are described in Jelley et al. U.S. Patent 2,322,027, issued June 15, 1943, and Fierke et al. U.S. Patent 2,801,- 171, issued July 30, 1957. As indicated above, the solvent should be selected so that it has no harmful effect upon the emulsion, and generally solvents or diluents which are miscible with Water are to be preferred. Water is a dispersing medium for many of the sensitizers of the invention. In a preferred embodiment, the sensitizer can be dissolved in a solvent, such as Water, ethanol, acetone, pyridine, N,N-dimethylformamide, etc., and added to the emulsion in this form. If desired, certain of the sensitizers can be prepared in finely-divided form and dispersed in water alone, or in the presence of a suitable dispersing agent (such as alkali metal salts of aromatic or aliphatic sulfonic acids) and added to the emulsion in this form. It is quite apparent that the sensitizers of our invention should have sufiicient water-dispersibility so that they can be absorbed to or associated with the grains of the silver halide present in the emulsion in sufficient amount to sensitize the emulsion. It is apparent that the optimum amount for each of the sensitizers will vary somewhat from emulsion to emulsion and from compound to compound. The optimum amount of any given sensitizer can be determined for any particular emulsion by running a series of tests in which the quantity of sensitizer is varied over a given range. Exposure of the treated emulsion in conventional photographic testing apparatus, such as an intensity scale sensitometer, will reveal the most advantageous concentrations for that sensitizer in that particular emulsion. Such matters are well understood by those skilled in the art.

In preparing photographic developing compositions containing the novel compounds of our invention, the bis-quaternary salts can be dissolved in a suitable solvent, such as water, and added to the developing composition from solution. Many of these novel quaternary salts can be added directly to the developing compositions containing any of the aforementioned developing agents, alkaline materials, such as sodium carbonate, sodium hydroxide, potassium carbonate, etc., preservatives, such as sodium sulfite, and any other conventional developer addenda, such as antifoggants and the like. Color developing compositions containing one of the aforementioned phenylenediamine color developing agents and our novel bis-quaternary salts can be used to develop negative or positive images in the presence of color-coupling compounds, such as the pyrazolones, phenols and openchain ketomethylene compounds. The color coupling component can be present either in the developing solution or in one or several layers of the photographic element being treated. The quantity of bis-quaternary salt used in the developing compositions can vary, depending upon black-and-white developing agent or color developing agent is being employed, etc. In general, the amount of bis-quaternary salt can vary from about 1 to 50 grams per liter of developing solution. The exact amount employed will also depend upon the solubility of the bisquaternary salt in the developing composition and the pH of the developing composition. In general, the pH of the developing solution will vary from about 9.0 to about 12.5.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

What We claim as our invention and desire secured by Letters Patent of the United States is:

1. The sulfone bis-quaternary salts represented by the following general formula:

wherein R and R each represents an alkylene group, d represents a positive integer of from 1 to 3, Q represents an organic quaternary ammonium group selected from the class consisting of pyridinium, picolinium, collidinium, N-methyl piperidinium, N-ethyl piperidinium, triethyl ammonium, diethylmethyl ammonium, tripropyl ammonium, diethylbutyl ammonium and N-methylrnorpholinium and X represents an acid anion selected from the class consisting of perchlorate, p-toluenesulfonate, benzenesulfonate, methylsulfate, ethylsulfate and bromide.

2. The sulfone bis-quaternary salts represented by the following general formula:

wherein d represents a positive integer of from 1 to 3, m and n each represents a positive integer of from 2 to 10, Q represents the non-metallic atoms necessary to complete a heterocyclic monoazine ring, selected from the class consisting of pyridine and piperidine rings and X represents an acid anion selected from the class consisting of perchlorate, p-toluenesulfonate, benzenesulfonate, methylsulfate, ethylsulfate and bromide.

4. The sulfone bis-quaternary salts represented by the following general formula:

123 R4 R R wherein R R and R each represents a lower alkyl group, d represents a positive integer of from 1 to 3, m and n each represents a positive integer of from 2 to 3 and X represents an acid anion selected from the class consisting of perchlorate, p-toluenesulfonate, benzenesulfonate, methylsulfate, ethylsulfate and bromide.

5. The compound represented by the following formula:

6. The compound represented by the following formula:

7. The compound represented by the following formula:

8. The compound represented by the following formula:

9. The compound represented by the following formula:

e e oanmonmsononnlsononnm 05115-20104 10. The compound represented by the following formula:

11. The compound represented by the following formula:

12. The compound represented by the following formula:

13. The compound represented by the following formula:

(p) CH3CH4S 03 03s (1 114-01130 14. The compound represented by the following formula:

15. The compound represented by the following formula:

CH CH3 16. The compound represented by the following formula:

C H: CH3

s NQonmsozronndsonomn n s -2x wherein d represents an integer of 2-10 and X represents an acid anion selected from the class consisting of perchlorate, p-toluenesulfonate, benzenesulfonate, methylsulfate, ethylsulfate and bromide.

References Cited UNITED STATES PATENTS 2,592,273 4/19'52 Goebel et a1. 260-567.6 2,623,902 3/ 1952 Crossby 260567.6 2,740,713 4/ 1956 Warren 96-65 2,938,793 5/1960 Goldberg et a1. 9665 3,061,437 10/1962 Burness 96-408 3,086,023 4/1963 Shore 260294.8 3,101,342 8/1963 Thomas 2602948 3,201,434 11/1960 Tesoro 260458 OTHER REFERENCES Noller, Chemistry of Organic Compounds, 2nd ed., Saunders (1957), p. 285. GD253-N65.

HENRY R. IILES, Primary Examiner.

ALAN L. ROTMAN, Assistant Examiner.

US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,1453 Dated July 1 1 969 Dona1d M. Burness, Kenneth C. Kennard and Bernard 0. C s

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

C' olurr1n 1 line 18, delete "h8L .,527" and insert --8h8,S27-.

Column 3, line 15, delete "components" and. insert ---coinpounds---.

Column 14., Example 2, change "C H %(CH S(CH S(CH C H -2ClO to --C5H5N(CH2)3S(CH2)1OS(CH2)3 c H -2c1o (+3 Column 5, Example 7, change "C H5%(CH2)6SO2(CH2EO2(CHZESOZ (CH2)5NC5H5' 2010 to "43 11 (cH s (cH kso (cH so (cH c H -2c10 Column 5, Example 10 change "o H %(cH s(cH S(CH SCH %C H ClO to ---c H @(cH s(cH s(cH soH %c H c10 Column 6, Example 15, change CH NQwHQ SwH 1 s (CH2)3 @011 Column 7 line g. should read 58 g. line 58, "ssage" should read stage line "(coupler)" should read (couplers) 22 3 UNITED STATES PATENT OFFICE- CERTIFICATE OF CORRECTION Patent No. Dated July 1, 1969 Inventor) Donald M. Burness, Kenneth C. Kennard & Bernard C Cossar It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shownbelow:

Column 6, Example 18, delete "3,1l -Dithia-3, 3,1Lp,1l tetraox0 1' hexadecane-1 16-bis(Nmethylpiperidinium p-toluenesulfonate) to -3,3,1L ,1L -tefir'aoxo3,1Lpdithia-1 ,1 6-bis-(N- methylpiperidinium p-toluenesulfonate)- Column 7, Example 19, delete "3, 1 M-Dithia-B, 3,1Lp, 1 h-tetr-aoxohexadecane- 1 ,1-bis-(diethylmethylammonium p-toluenesulfonate)" to -3, 3,1L;.,1Lp-tetraoxo3, 1 L1,-dithia1 ,16-bis-(diethylmethylammonium p-toluenesulfonate) Column 7, Example 19, change 9 O SC H CH (p (9 o so H -cH Signe and sealer this 9th day of May 1.917.

SEAL) At m :1 t:

EDWARD ELFLETCHERJR. ROBERT GOTTSCHALK Antes: Ling Officer COIIL HjGSlODE'P of Pa Dents 

1. THE SULFONE BIS-QUATERNARY SALTS REPRESENTED BY THE FOLLOWING GENERAL FORMULA: 